Laminates of ethylene vinyl acetate polymers and polymers of vinylidene chloride

ABSTRACT

A multiply laminate useful as a packaging film having a first layer of a cross linked ethylene vinyl acetate polymer, a directly joined middle layer of a polymer of vinylidene chloride and a third layer directly joined to the middle layer of an ethylene/vinyl acetate polymer. Especially preferred for the middle layer are blends of emulsion polymerized and suspension polymerized vinylidene chloride and an epoxy resin.

United States Patent [191 Brax et al.

[ 1 LAMINATES OF ETHYLENE VINYL ACETATE POLYMERS AND POLYMERS OF VINYLIDENE CHLORIDE [75] Inventors: Harri J. Brax; Joseph F. Porinchak,

both of Spartanburg; Alan S. Weinberg, Greenville, all of S.C.

[73] Assignee: W. R. Grace & Co., Duncan, S.C. [22] Filed: Mar. 30, 1971 i [21] Appl. No.: 129,501

[52] US. Cl 138/137, 99/174, 138/141, 138/177,161/184, 161/254, 161/404 [51] Int. Cl... B32b 27/30, B32b 27/38, 1365b 25/06 [58] Field of Search 138/177, 141, 146, 138/137; 161/184, 252, 254, 256, 404,139,

[56] References Cited UNITED STATES PATENTS 3,475,248 10/1969 Brasure 156/229 June 26, 1973 3,524,795 8/1970 Peterson 161/252 X 3,542,902 11/1970 Dunion et al. 161/184 X 3,558,330 1/1971 Widiger et a]. 99/174 3,647,485 3/1972 Seiferth et al. 99/174 3,650,775 3/1972 Simon et a], 161/252 X 3,682,767 8/1972 Britton et a1 161/254 Primary Examiner-J-larold Ansher AttorneyJohn J. Toney, William D. Lee, Jr. and Edward J. Hanson, Jr.

57 ABSTRACT A multiply laminate useful as a packaging film having a first layer of a cross linked ethylene vinyl acetate polymer, a directly joined middle layer of a polymer of vinylidene chloride and a third layer directly joined to the middle layer of an ethylene/vinyl acetate polymer. Especially preferred for the middle layer are blends of emulsion polymerized and suspension polymerized vinylidene chloride and an epoxy resin.

4 Claims, 5 Drawing Figures PAIENIEOJux2s ms 3.741. 253

FIG. 2

IIIIIIIIIII FIG. 4

38 36 3432 3028 2624 2220 I8 HIGH REF. LOW

FIG. 5

LAMINATES OF ETHYLENE VINYL ACETATE POLYMERS AND POLYMERS OF VINYLIDENE CHLORIDE BACKGROUND OF THE INVENTION This invention relates to compositions for forming films, coatings, and laminates formed from the compositions, methods for producing them and the uses of the materials in packaging products, especially food products such as bone-in fresh red meats.

In the past barrier laminates containing a barrier layer of saran together with layers of a copolymer of ethylene vinyl acetate with an outer layer of polyethylene have been used to package foodstuffs including meats as shown in US. Pat. No. 3,549,389. Other saran to polyethylene laminates and the like have also been known as shown by Canadian Pat. No. 743,021; and U. S. Pat. Nos. 3,031,332; 2,968,576 and 2,955, 869. However with such laminates it has generally been necessary to employ bone puncture protective means such as those shown in U. S. Pat. No. 2,891,870. In addition, it may be seen that the laminates of the prior art have required separate plies to provide the necessary abuse resistance of one lamina, the necessary adhesive characteristics of still other laminas and the barrier properties of still another lamina or various special treatments to obtain suitable adhesion characteristics between the plies. In addition ethylene coplymers having a substantial vinyl acetate content have not been believed to be satisfactory for an outer or inner lamina or coating that must be abuse resistant. Generally only those ethylene vinyl acetate copolymers having vinyl acetate contents below 5 percent have been felt to be at all suitable for such use. These are only a few of the shortcomings of the prior art.

There is therefore a need for a laminate of simplified construction having all the necessary characteristics for packaging bone-in cuts of meat and a wide variety of other items without the use of special packaging aids.

SUMMARY OF THE INVENTION By an aspect of the invention a method for producing an abuse resistant polymer film is provided that includes forming the film from a polymer material having a narrow molecular weight distribution with a generally random molecular weight distribution therebetween. The general weight distribution is preferably approximately that of the standard bell curve. The preferred polymer material is based on ethylene vinyl acetate containing 5-20 percent vinyl acetate. More preferably the polymer is a copolymer of ethylene and vinyl acetate containing 8-12 percent vinyl acetate.

The above described polymer material is preferably formed into the outer ply of a laminate. This outer ply could be an inside ply or coating in a bag, for example, by outside ply it is meant that it is a surface or exposed ply that may be subject to external abuse, abuse by an object engaging the coating. The laminate preferably includes an inside ply of a barrier material, preferably one based on saran. The saran is preferably a new saran composition comprising a polymer of vinylidene chloride having at least 50 percent vinylidene chloride and being a blend of 5-40 percent suspension polymer and 60-95 percent emulsion polymer, preferably with an epoxy resin blended therewith in an amount of 2-10 percent.

An alternate inside barrier ply is a melt extruded layer of saran that is a liquid coating grade of vinylidene chloride and vinyl chloride copolymer having 5-15 percent vinyl chloride. In a preferred form the liquid coating grade copolymer of vinylidene chloride and vinyl chloride is present in an amount of from 5-100 percent with the remainder being 2-10 percent epoxy resin and melt extrusion grade saran.

By another aspect of theinvention improved films and laminates are provided having the features described above with respect to the method of their creation.

An aspect of the invention provides a very advantageous method of manufacturing a three-ply laminate having the inside barrier layer (described above) sandwiched between outside plies of the outer ply described above. By this method the third ply is melt extruded as a tubular film, solidified and cross linked, preferably by irradiation at a dosage of 2-15 me'gareps. The irradiated tube is passed to a coating die where the second ply is melt extruded as a second tubular film, coated on and directly adhered to the irradiated tube forming a two-ply tubular film. The two-ply tubular film is passed to a coating die, preferably while still hot, and the first ply is extruded as a tubular film coated on and directly adhered to the second tubular film forming a three-ply tubular film laminate. The three-ply tubular film is solidified and the tubing is stretched biaxially and thus biaxially oriented to provide a shrink tension of from 200-500 psi and a free shrink of at least 40 percent at 205F.

By still another aspect of the invention a method is provided for preventing punctures and leaks in packaging bone-in cuts of meat in heat sealable plastic films. The method includes coating the inside of the'plastic film that will be exposed to the cut of meat and bone with a polymer material that is solid at room temperature and has a narrow molecular weight distribution. The meat is enclosed in the film to form a package and then heat is applied to the package to shrink the film against the bone-in cut of meat.

It is therefore an object of this invention to provide compositions of wide utility, having both advantageous manufacturing utility and end use utility, and providing end products that have not only wide utility but superior performance and low cost.

The invention may be better understood by reference to the following detailed description and drawings in which:

FIG. 1 is a schematic diagram of a preferred method for carrying out the invention;

FIG. 2 is a cross section of the die head used in the present invention;

FIG. 3 is a view taken along line 3-3 of FIG. 2;

FIG. 4 is a cross sectional view of the laminate film of the present invention; and

FIG. 5 is a graph of molecular weights.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Unless otherwise identified specifically herein, percentage contents refer to the weight percent of each ingredient in the total composition including all additives. Thus, when a composition includes additional materials not affecting the essential character such as stabilizers, pigmenting agents, processing aids such as waxes, deodorizing agents, anti-static agents, antiblocking agents, etc., these materials will be understood to slightly reduce the actual content of recited materials when they are given on the basis of their percentage content in the composition.

When a polymer material is set forth as being based on ethylene and vinyl acetate, this indicates that the ethylene and vinyl acetate are polymerized but that other ingredients may be included in the polymer. Thus the polymer could be a terpolymer or some other polymer than a copolyrner so long as the predominant polymer portions are those recited. The same is true of the saran or vinylidene chloride polymers. The term saran is used herein in its normal commercial sense with reference to polymers made by polymerizing vinylidene chloride and vinyl chloride. Additional monomers suitable for polymerization with the vinyl chloride and vinylidene chloride to provide a barrier material are many and well known and therefore are not listed here. When a barrier layer is referred to broadly, vinylidene chloride polymers are those most commonly used but in special instances other materials such as vinyl chloride polymers, fluorocarbon polymers and many others may be used. As is well known, many of the polymer materials, such as those referred, to include additives that are not considered to change the essential character of the material. A number of the additives are listed above.

Referring now to FIG. 1, a conventional extruder 9 is shown into which is fed a polymer material having a narrow molecular weight distribution, preferably a polymer material based on ethylene and vinyl acetate having 5-20 percent vinyl acetate, most preferably a copolymer of ethylene and vinyl acetate having 5-20 percent vinyl acetate, more preferably 8-12 percent vinyl acetate. The molecular weight distribution of the polymer is preferably a generally random molecular weight distribution most preferably in the general distribution of the standard bell curve distribution which is represented by Line A of FIG. 5. It may be observed that this is not an exact bell curve which would be unusual in a commercial polymer material.

Molecular weight distribution as used herein is determined by use of a gel! permeation chromatograph. It has been found that a polymer having the molecular weight distribution of curve A in FIG. 5 is satisfactory while a polymer having a molecular weight distribution 'of curve B is unsatisfactory for the films of this invention. These curves were analyzed by standard statistical techniques and the following determinations made:

Curve A Curve B standard deviation (sd) 3.07 3.65 Number Average Molecular Weight (M) 28,96 27.89 Coefficient of Variation (100) (sd)/M l0.62 13.08 Area under curve, il0% of M 64.32 50.72

about 28 (curves A&B) that the area under the distribution curve should be greater than that shown by curve B in an area bounded by an abscissa of i 10 percent of the number average molecular weight, a lower ordinate of o and the upper ordinates represented by the distribution curve. Preferably the area will be the similar area for curve A less 50 percent, more preferably 25 percent, of the difference in these areas for curve A and curve B. In other areas for polymers having a number average molecular weight of about 28, the area is greater than 50.72, preferably greater than 57.57, more preferably greater than 60.94.

The tubing 10 is extruded downwardly from die head 1.1whisk.isfsqlttvmstt -3 extruded tubing is 10-30 mils thick, morepref erably 15-25 mariner. After cooling or quenching by water spray from cooling ring 12, the tubing is collapsed by pinch rollers 13 and is fed through an irradiation vault 14 surrounded by shielding 15 where it is irradiated with electrons from an iron core transformer accelerator 16. Other accelerators such as a Vander Graft or resonating transformer may be used. The radiation is not limited to electrons from an accelerator since any ionizing radiation may be used. The unit or radiation employed here is the RAD which is defined as the amount of radiation which will dissipate 100 ergs of energy per gram of irradiated material by ionizing particles. The MR is one million l0) RAD.

In special instances it may be desirable to cross link the polymer through other means such as chemical cross linking agents. In the preferred procedure, how ever, irradiation is employed and preferably as described.

The time of irradiation of the ethylene vinyl acetate tubing 10 is not critical but need only be enough to give the required dosage to effect the desired amount of cross linking. In the present embodiment the tubing 10 is preferably irradiated at a dosage of 2-15 MR and more preferably at a dosage of 2-10 MR.

The tubing 10 is guided through the irradiation vault 14 by rollers 17. After irradiation the tubing 10 goes through pinch rollers 18 following which it is slightly inflated by a trapped bubble 20. The tubing is not significantly stretched longitudinally as the rollers 18 are driven at about the same speed as rollers 13. The tubing is inflated only enough to provide a substantially circular tubing without significant transverse orientation.

The slightly inflated irradiated tubing 10 is passed through vacuum chamber 21 to a laminating or coating die 22. A second tubular film 23 is melt extruded from the coating die 22 and coated onto and directly adhered to the irradiated tube 10 to form a two-ply tubular film or laminate 24. The second tubular film 23 is preferably a barrier ply. The barrier ply is preferably a polymer material based on saran or a polymer of vinylidene having at least 50 percent vinylidene and more preferably a polymer or copolymer of vinylidene chloride and vinyl chloride having 5-40 percent vinyl chloride, most preferably 15-30 percent vinyl chloride. This composition is preferably 5-40 percent suspension polymer and 60-95 percent emulsion polymer, more preferably 5-15 percent suspension polymer and -95 percent emulsion polymer. The preferred barrier layer also includes in combination therewith 2-10 percent epoxy resin more preferably 4-6 percent epoxy resin. Thus the preferred barrier layer is a saran film of a corq xmsr 0 v ny de q llpr s endt in l chloride ing 5-40 percent vinyl chloride combined with per cent 2-10 percent epoxy resin with the saran being a blend of from 5-40 percent suspension polymer and 60-95 percent emulsion polymer. The more preferred barrier film would be a saran that is a vinylidene chloride/vinyl chloride having -30 percent vinyl chloride combined with 4-6 percent epoxy resin, the copolymer being a blend of 5-15 percent suspension polymer and 85-95 percent emulsion polymer.

As used herein epoxy resin means a high viscosity thermoset resin as distinct from epoxidized oils which are the usual epoxy plasticizers and are normally formed of epoxidized natural oil and are much less viscous.

It is quite unexpected that the blend of emulsion and suspension resins, particularly those of the saran or vinylidene type, can be melt extruded and formed into a good quality biaxially oriented film. Normally the suspension resin would be expected to cause gels to form in the emulsion resin during extrusion. In the present case, however, the suspension polymer seems to act as a stabilizer rather than causing gels in the emulsion polymer film. While we would not want to be held to the following beliefs, it is believed that the suspension polymer melts more slowly in the barrel of the extruder and acts as a scouring agent during the passage of the blend through the extruder preventing a build up of the saran on the extruder barrel and its decomposition. The emulsion polymer tends to stick when it melts and the suspension polymer acts somewhat like ball bearings moving it along. Of course, prior to extrusion and adjacent the die the suspension polymer is also melted. It has been found that going above percent in suspension polymer content usually causes difficulty with film orientation. Only with very careful handling is it possible to go up to 40 percent suspension polymer content. Crystals form more rapidly in a suspension polymer film. Thus the suspension polymer acts as a contaminant in the emulsion polymer in the sense that the suspension polymer' crystallizes so rapidly that it does not permit sufficient time to achieve sufficient drawdown during the orientation step.

We have found it possible to operate at extrusion temperatures between the normal processing conditions for the two polymers, in other words between 280F and 340F. It was not originally thought that the blended materials would be compatible in the melted polymer state because of the differential melting rates between the two polymers.

Thus the extruder is preferably operated at a barrel temperature of 200-320F, more preferably 250-300F and the extrusion die is preferably operated at a temperature of from 280-340F more preferably 295-3 15F. The extruded tubing is l-5 mils thick, more preferably 2-4 mils thick.

The extruder is conventional, e.g., a standard 3% inch extruder. The die 22 is a circular cross head die which has an adaptor 26 (FIG. 2) attached thereto to provide in its preferred form a 3% inch opening 27 for the slightly inflated tubing 10.

The details of the die 22 may be better appreciated by referring to FIGS. 2 and 3. The opening 27 through which the inflated substrate passes has been formed through mandrel 28 which is attached to the die housing 29. The path of the molten coating material 23 is indicated by the arrows in FIGS. 2 and 3. The vacuum chamber 21 puts a mild vacuum, e.g., in the range of from 0 to about 25 inches of water, on the die 22 to draw or pull up the extruded film 23 while it is still molten against the inflated tubing 10 to prevent the formation of occluded bubbles in the laminate 24. The vacuum chamber 22 can simply consist of the cylindrical housing whose inner diameter closely conforms to the outer diameter of the inflated tubing. A vacuum can be applied through outlet 30 by a conventional vacuum hose.

An alternate preferred barrier material is a saran liquid coating material of the type used to solvent or emulsion coat with saran rather than melt coat. This material can be substituted for the suspension polymerized saran of the previously described preferred barrier composition. It is believed that this liquid coating vinylidene polymer material acts in exactly the opposite manner from the suspension polymer saran, it has a lower melt viscosity and enhances the blends flow in the manner of a lubricating effect. Liquid coating sarans are not thought of as being melt extrudable. In still other instances it has been found possible to substitute the liquid coating saran for all of the saran in the composition and melt extrude the composition and form a good film which has indeed been surprising. the liquid coating sarans are also usually emulsion polymerized but have established a distinctive character in the art.

The two-ply film 24 is passed to the coating or laminating die 32 preferably while still hot. In a discontinuous process it would be possible to cool or quench the tubing 24 prior to passing it to the second coating die 32 but this would also necessitate, in the usual instance, both a reinflation and a reheating of the tubing to obtain an excellent bond between the second ply and the first ply. The first ply considering the tubing from the outside thereof would be both an outer ply and the outer ply of the tubing.

A first tubular film, the third extruded in sequence, is melt extruded from the coating die 32 and coated on and directly adhered to the two-ply tubular film 24 to form a three-ply tubular film 34. Tubular film 33 is preferably of a composition chosen from those given when discussing tubular film 10 above. Although not necessarily of the same identical composition as tubular film 10, it would normally be identical as a matter of convenience in compounding. It may be seen that the coating process at die 32 is the same as that at die 22. The vacuum chamber 36 serves the same function as the vacuum chamber 21 and operates in the same manner with a vacuum being applied through outlet 37. The tubular film or ply 33 is 3-15 mils thick, more preferably 4-12 mils thic The three-ply tubular film laminate 34 is cooled or quenched by the water spray from cooling ring 39. The water is normally at about 45F. Pinch rollers 40 then collapse the three-ply tubular film and the film is rolled onto wind-up roll 41. Alternatively in a continuous pro; cess the film would not be rolled up onto wind-up roll 41 but would be delivered directly to the next step in the process sequence to stretch the film.

As shown in FIG. 1 a pay-out roll 42, which would be a previously prepared wound-up roll 41, is unwound over guide roll 43. The laminate 34 is substantially unstretched and unoriented as it passes over the guide roll 43. The film passes from guide roll 43 into a hot water bath tank 44 containing water 45. The preferred reheating temperature or hot water temperature is 160-212F, more preferably l-205F. The collapsed three-ply tubular film is submerged in the hot water for a retention time of at least about 5 seconds.

This is generally necessary to bring the film up to the desired temperature for orientation stretching. A typical retention time in the water bath is about 20 seconds. Guide rolls 47 guide the collapsed tubing through the water bath 45.

After the temperature of the three lamina of the tubing are adjusted to their proper orientation level, the bubble 46 is blown and the film is stretched in both the transverse and longitudinal directions in a preferred ratio of 1:15 1:6, more preferably 1:2 1:4 which would be a biaxial orientation of 122.25 l:3.60 and 1:4 l:l6, respectively. Each of the coatings and the substrate are reduced substantially in equal proportions. It may be seen that the laminate is orientable out of hot water to produce the desired physical characteristics. The bubble 46 is maintained between pinch rolls 48 and 49. The tubing is collapsed by rollers 50 and the laminate is conveyed through pinch rollers 49 and across guide roll 51 and rolled onto wind-up roll 52. Idler roll 53 assures a good wind up.

In FIG. 4, a cross section of the laminate 34 is illustrated, showing the third protective outer ply of plastic film 10 which is of course the intermediate ply of the tubing, barrier layer coating or inside ply of plastic film 23 and the first ply or coating of plastic film 33 which forms an outerv protective ply for the laminate and outer protective coating of the tubular member. These three plies are directly joined without intermediate plies to form the three-ply laminate. The compositions of these plies will not be repeated here as they are clear from the previous description. After orientation the laminate film, which is shown in FIG. 4, has a preferred thickness of the third ply 10 of 0.5 to mils, more preferably l to 2 mils, thickness of the intermediate ply 23 of 005-2 mils, more preferably 0.1-.5 mils and a thickness of the outer ply 33 of 0.1-4 mils, more preferably O.25-l mils. The laminate has a preferred shrink tension of from 200-400 psi and a free shrink of at least 40 percent more preferably at least 50 percent, 1 at 205F and a free shrink of at least 20 percent, more preferably at least 30 percent, at 185F. v

In another preferred procedure of producing the laminate, the second and third applied coatings can be ccextruded onto the preformed tubing from a coextrusion die. This would produce the same end laminate but is a somewhat more difficult procedure.

The tubular film produced from the tubing of this invention produces an excellent barrier bag, the ply bonding to itself very well at temperatures between 200F and 350F without distorting substantially when the seals are produced with a thermal impulse sealer.

The ply 10 also gives excellent puncture strength.

The thin saran based barrier layer provides the necessary barrier characteristics with a minimum thickness and expense. The outer layer of unirradiated polyethylene copolymer give high low temperature abuse resistance and improved tear resistance.

Ah advantageous method for employing bags made from the tubing of this invention is shown in U. S. Pat. No. 3,552,090. The bags are suitably closed after vacuumizing by clipping, for example, as shown in U. S. Pat. No. 3,383,746. A suitable vacuumizing device is shown in U. S. Pat. Application Ser. No. 844,883, filed July 25, 1969, Dave L. Owen, inventor, now U.S. Pat No. 3,628,526. The just referred to patents and applications are all assigned to thesame assignee as the present application.

The laminates optimum use and the use for which it was specifically designed, although it obviously would have many other uses, is' as a packaging material for bone-in cuts of fresh red meat having exposed bones. When so employed the preferred and the most preferred laminate which is formed of the preferred and most preferred compositions is of almost critical importance. While an inferior laminate could be used employing for example a different barrier layer, this is at a substantial cost in processing ability and quality. The laminate is also nontoxic and food approved. It will be understood that when a bag is employed to package a piece of fresh red meat that has not been frozen and is not to be frozen'but will be packaged and retained at low temperatures, e.g., 32-45F, the laminate encloses the bone-in cut of meat and exposed bones impinge against the inside protective ply of the bag which is an outside protective ply of the laminate.

In the preferred process, the bone-in meat is inserted into the three-ply laminate which is biaxially oriented and heat shrinkable. The laminate thus encloses a 1 the meat and with the bone-in cut of meat forms a package that will preserve the meat for an extended period of time.

This invention provides an excellent means of preventing punctures and leake rs in packaging bone-in cuts of meat in heat shrinkable plastic films because the inside coating of the plastic film which is exposed to the meat and bone is a polymer material having a substantial narrow molecular weight distribution that is solid at room temperature. The preferred polymer material for this coating is the composition given with respect to the first ply already described. By enclosing the meat in this film and forming a package and then applying heat to the package to shrink the film against the bone-in cut of meat, an excellent package can be formed. By using such a film with a good barrier layer, the meat may be protected in storage for extended periods of time.

In the preferred form of this invention, it is important that the irradiation dosage be within the confines set because this yields an adherent coating that has sufficient tensile strength to give good processability, good bone-puncture resistance and good orientability. Irradiation should be sufficient to increase the tensile strength without deteriorating elongation very much, as the material must stretch with the bone when packaging bone-in cuts of fresh red-meat. At the same time it is desirable that the bag cling to soft meat and to bone wherever the bone sticks out of the meat. Fresh red meat can be soft and allow the bone to move or float within it. If the film is irradiated too much, the elongation goes down and the bone will go right through on impact. If the vinyl acetate content is above that specified, the melting point of the polymer decreases adversely affecting the high temperature properties required for shrink packaging.

In addition to losing abuse resistance at shrink tunnel temperatures, the seals delaminate'when the vinyl'acetate content goes up much above 18 percent on this particular laminate. If the vinyl acetate drops down below 5 percent, the low temperature elasticity decreases and the modulus of elasticity increases to such an extent that the bag no longer functions as required for an efficient packaging operation.

The laminate has a number of very desirable characteristics, in its preferred form, including good shrinkability at a moderately raised temperature, an elongation of at least 50 percent, more preferably 100-125 percent, an oxygen transmission rate of no more than 70 cc/(l sq.m./24 hrs./l atm.) at 73F, percent r.h. (A.S.T.M. D 1434); and more preferably no more than 25 cc/(l sq.m.l24 hrs./ 1 atm.) at 73F, 0 percent r.h. (A.S.T.M. D 1434). In its preferred form the film has a ball burst impact resistance of at least 25 cm-kg.

Various aspects of the invention can be employed independently or in other combinations with advantage over the materials normally so employed. The saran compositions can be formed into independent films. The compositions have the superior extrusion characteristics already enumerated whether being melt extrusion coated or melt extruded as independent self supporting films. Of course, to be self supporting the extruded saran film would have to be at least about 2-3 mils thick if extruded as a tubing using normal saran tube extrusion techniques. In addition it has been found that the saran film formed from a blend of emulsion and suspension polymerized saran has unexpected tear and puncture resistance for an oriented film when compared to existing known saran films.

In certain instances it might be desirable to substitute another polymer for the outer laminate or ply in a bag. This is the ply that needs to be resistant to scuff and tear abuse as against puncture resistance which is important for the inside ply of the preferred bag to be used in packaging bone-in fresh red meat. These poly mers should also have relatively narrow molecular weight distributions, preferably with a generally ran dom molecular weight distribution, most preferably in the general distribution of the standard bell curve. Examples of such polymers are polypropylene, polyamids, polyesters and the like, and copolymers, terpolymers and other polymers of such materials. Such groups of coating polymers are well known, however, the proper choosing of the polymer material with the right molecular weight characteristics is an aspect of this invention. Of course, in certain applications the outer lamina or even the inner lamina might not need the advantages of this invention but the other lamina may be necessary and so the aspects of the invention are claimed both in the combination essential for best quality for the preferred application and independently for other applications or uses.

This invention is further illustrated by the following example:

EXAMPLE I Following the procedure as schematically outlined in F IG. 1, an ethylene vinyl acetate copolymer containing percent vinyl acetate having a melt index of about 2 and a molecular weight distribution as shown by line A of FIG. 5 and sold as UE 637 by U. S. Industrial Chemicals Division of National Distillers, is fed into the extruder hopper of extruder 9. The extruder is a 3.5 inch extruder and is operated at the following temperatures: rear zone, 250F; mid-barrel 270F; front barrel, 290F; adaptor, 300F; and die, 330F. The screw rpm is 37 and the pressure is 3,800 psi. The die diameter is 3.5 inches and the tubing circumference produced is 8 inches. The water from the cooling ring 12 is 45F. The

pinch rolls 13 are operated at 35 feet per minute and the tubing thickness is approximately 18 mils.

The collapsed tubing is passed through an irradiation unit such as that depicted in FIG. 1 operated at 500 KEV, 20 MA and a speed of 35 feet per minute. Four passes are made and the tubing receives a dosage of about 6 megarads.

The irradiated substrate film is then passed to a coating die 22 where it is coated with a barrier material. The composition of the barrier layer is a lightly plasticized copolymer of vinylidene chloride and vinyl chloride. The copolymer is a mixture of 10 percent suspension polymerized and 90 percent emulsion polymerized copolymer. The emulsion polymerized copolymer consists of about percent vinylidene chloride and 30 percent vinyl chloride and the suspension polymerized copolymer consists of about percent vinylidene chloride and 20 percent vinyl chloride. These materials were purchased from Dow Chemical Company and are sold as UP 925 (emulsion polymerized resin) and SP 489 (suspension polymerized resin). The composition includes 5 percent of an epichlorohydrin/bisphenol A epoxy resin sold as EPON resin 828 by the Shell Chemical Company. It also includes about 0.5 percent of a microcrystalline paraffin wax purchased from Sun Chemical Company and sold as Wax 5512. The three resins are blendedin a high speed, high intensity Prodex-I-Ienschel blender and the blend is fed into the hopper of extruder 25 which is a 2 inch Prodex extruder operated with a cross head die of the type illustrated in FIGS. 2 and 3. The second extruder is operated at the following temperatures: rear zone, 210F; mid-barrel, 260F; front barrel, 300F; adaptor, 285F; and die 320F. The screw rpm is 34 and the pressure is 5,500 psi. The die diameter is 3.5 inches and the tubing circumference is 8 inches. The top rolls 18 are operated at 35 fpm and the coating thickness is approximately 3 mils.

The second coating resin applied at extruder 35 is identical to the resin added to the hopper of the first extruder 9 and the extruder operating conditions are rear zone, 250F; mid-barrel, 270F; front barrel, 380F; adaptor, 440F; and die 45 0F. In other respects the extruders operation is the same as that set for extruder 9. The coating die 32 is of the same design as the coating die 22. The bottom rolls 40 are operated at 36 fpm and the water from the chill ring 39 is at 45F. The coating thickness is approximately 6 mils.

Biaxial orientation is carried out by preheatingin water at about F as shown at 44 of FIG. 1 and passing the thus heated tubing through pinch rolls operating at 19 fpm to deflate rolls operating at 70 fpm and blowing the 4 inch wide tubing to produce a film width of approximately 16 inches with a film thickness of approximately 2.4 mils. This tubing is then rolled up on a storage roll which is then converted into bags by sealing the tubing transversely at intervals to form bottoms in conventional manner and severing the tubing into desired bag lengths.

EXAMPLE II hexyl diphenyl phosphate plasticizer purchased from Monsanto and identified as Santicizer 141 and reducing the epoxy resin content to 3 percent.

EXAMPLE III The procedure of Example I was repeated except the barrier layer composition was 66 percent saran resin UP 925, 30 percent of a liquid coating saran resin purchased from Dow Chemical Company and sold as OX 2168, 2 percent Epon resin 828 and 2 percent Santicizer 141.

EXAMPLE IV The procedure of Example III was repeated except the saran in the barrier layer composition was all QX 2168.

EXAMPLES V & VI

The procedures of Examples III and IV were repeated except a liquid coating saran sold by W. R. Grace & Co. as Daran CR 6795-H was substituted for the QX 2168.

EXAMPLE VII The procedure of Example I was repeated except 5 percent of an epoxidized soybean oil (not an epoxy resin as defined herein) sold by Swift & Co. as Epoxol 7-4 was substituted for the 5 percent epoxy resin.

EXAMPLE VIII The procedure of Example VII was repeated except 4 percent of 2-ethyl hexy] diphenyl phosphate plasticizer and 1 percent magnesium oxide were substituted for the 5 percent epoxy resin.

EXAMPLE IX The procedure of Example I was repeated except a mixture of 53.3 percent by weight of isotactic polypropylene (Novamont* Novamont is a trademark of the Novamont Corp.) F007), 33.3 percent polybutene-l (Mob il* Mobil is a trademark of the Mobil Oil Co.) PB 103) and 13.3 percent atactic polypropylene (Novamont' Lot 2030) is used to form the third layer. The The atactic and isotactic polypropylene are first added in proper proportion to a banbury mixer and melt blended for approximately 8 minutes at 400F. and then extruded into a sheet which is diced into pellets. These pellets are combined with pellets of polybutene-l in a rotating drum and this admixture is charged to the hopper of extruder 35. Extruder 35 is operated at the following temperatures: rear zone, 385F; midzone 400F, forward zone, 450F; adaptor, 400"F; and die, 425F.

EXAMPLE X The saran composition of Example II was extruded as a self supporting single layer film under the extrusion conditions set forth in Example II except 4 percent of the epoxy resin was used, and the ,UP 925 resin content was reduced 1 percent, an interior coating of propylene glycol was applied interiorly to prevent sticking when the tubing is collapsed prior to its biaxial orientation and the process was continuous, the bubble 46 being formed after collapse but without rolling the tubing up. In addition, the water bath was maintained at about IF, the extrusion gauge at about mils and the biaxially oriented gauge at'about 0.75 mils after a total orientation stretch ratio of about 12:1 biaxially. The film was found to have unexpected tear and puncture resistance for an oriented film when compared to existing known saran films.

PACKAGE ABUSE TESTS The following test procedure was carried out, all test bags were precoded and conditioned for 24 hours at 4550F. The bags are randomized and used to package full bone-in ribs weighing 25-30 pounds. The bags are 16 inches wide by 30 or 32 inches deep. The packages were vacuumized, clipped, shrunk and dried in an are stored at 38F for 24 hours and then shakes for 7.5

minutes at l g. on a L.A.B. Vibration tester* Trademark of LAB. Corporation) sincrenois motion to simulate a l25-mile truck shipment.

In both tests the packages are pumped with air and submerged under water to determine leakage which is rated as failure.

TABLE 1 Bone Shipping Oxygen puncture abuse barrier, Lamiresistance, (bone-in), cc. (1 sq. nate percent percent m./24 hrs.l Bag gauge survival survival 1 atm.)

Made in substantial conformance with Example I 2. 4 82 45 D0 2. 7 73 92 40-45 Made in substantial conformance with Example II 2. 0 63 35 Standard Saran bag produced by W. R. Grace & Co 1. n 25 45 150 Standard Saran bag purchased from Union Carbide 23.3 36. 6 150 We claim: 1. A multiply laminatecomprising A. a first ply having a thickness of 0.5 5.0 mils and comprising a cross linked polymer of ethylene and vinyl acetate having 5 to 20 percent by weight of vinyl acetate, and V B. a second ply directly joined to said first ply having a thickness of 0.05 to 2 mils comprising a polymer of vinylidene chloride and vinyl chloride having 5 to 40 percent by weight of vinyl chloride, and

C. a third ply directly joined to said second ply having a thickness of 0.1 to 4.0 mils and comprising a polymer of ethylene and vinyl acetate having 5 to 20 percent by weight of vinyl acetate.

2. The laminate of claim 1 wherein said second ply comprises a blend of 5 to 40 percent by weight of suspension polymerized polymer and 60 to 95 percent by weight of emulsion polymerized polymer.

3. The laminate of claim 1 wherein said second ply comprises a blend of a polymer of vinylidene chloride and vinyl chloride and 2 to 10 percent by weight based on the blend weight of an epoxy resin.

4. A tubular thermoplastic multiply laminate suitable for packaging which has been biaxially oriented to provide a shrink tension of 200 to 400 psi and a free shrink of at least 40 percent at 205F and which has an oxygen transmission rate of no more than 70 cc (m /24hr/ l atmosphere) at 73F, said laminate comprising A. An inner first ply having a thickness of l to 2 mils and comprising an irradiated copolymer of ethylene and vinyl acetate having 5 to 20 percent by weight of vinyl acetate, said first ply having been irradiated to a dosage of 2 to megarads, and B. A second ply directly joined to said first ply having a thickness of 0.1 to 0.5 mils comprising a blend of l. a mixture of 5 to 15 percent by weight of a polymer of vinylidene chloride and vinyl chloride prepared by suspension polymerization and 85 to 

2. The laminate of claim 1 wherein said second ply comprises a blend of 5 to 40 percent by weight of suspension polymerized polymer and 60 to 95 percent by weight of emulsion polymerized polymer.
 2. 4 to 6 percent by weight based on the blend weight of an epichlorohydrin/bisphenol A epoxy resin, and C. An outer third ply directly joined to said second ply having a thickness of 0.25 to 1.0 mils and comprising a copolymer of ethylene and vinyl acetate having 5 to 20 percent by weight of vinyl acetate.
 3. The laminate of claim 1 wherein said second ply comprises a blend of a polymer of vinylidene chloride and vinyl chloride and 2 to 10 percent by weight based on the blend weight of an epoxy resin.
 4. A tubular thermoplastic multiply laminate suitable for packaging which has been biaxially oriented to provide a shrink tension of 200 to 400 psi and a free shrink of at least 40 percent at 205*F and which has an oxygen transmission rate of no more than 70 cc (m2/24hr/1 atmosphere) at 73*F, said laminate comprising A. An inner first ply having a thickness of 1 to 2 mils and comprising an irradiated copolymer of ethylene and vinyl acetate having 5 to 20 percent by weight of vinyl acetate, said first ply having been irradiated to a dosage of 2 to 15 megarads, and B. A second ply directly joined to said first ply having a thickness of 0.1 to 0.5 mils comprising a blend of 